Fungicidal azolylethane derivatives

ABSTRACT

Azolylethane derivatives of the formula I ##STR1## where A and R 1  are each alkyl, phenyl, biphenyl, naphthyl, benzyl, cycloalkyl, alkoxy, alkylthio, phenoxy, benzyloxy, phenylthio, methoxycarbonylethyl or hetaryl, these radicals being substituted or unsubstituted, 
     D is halogen, alkoxy, alkylthio, phenylthio or phenoxy, these radicals being substituted or unsubstituted, 
     X is CH or N, 
     plant-tolerated acid addition salts and metal complex compounds thereof, and fungicides containing these compounds.

The present invention relates to novel useful azolylethane derivativeshaving a fungicidal action, fungicides containing these derivatives andmethods for controlling fungi with these compounds.

It is known that azolylethane derivatives, e.g.1-(1,2,4-triazol-1-yl)-1-phenylthio-2-methyl-2-phenyl-propane or1-(1,2,4-triazol-1-yl)-1-(4-chlorophenylthio)-2-methyl-2-phenylpropane(EP 91 219) or 1-methoxy-1-(1,2,4-triazol-1-yl)-2-phenylethane (DE 26 40823), can be used as fungicides. However, their action isunsatisfactory.

It is an object of the present invention to provide novel compoundshaving improved biological activity.

We have found that novel azolylethane derivatives of the general formulaI ##STR2## where A and R¹ are identical or different and are each C₁ -C₈-alkyl, phenyl, biphenyl, naphthyl, benzyl, C₃ -C₆ -cyclo-alkyl, C₁ -C₈-alkoxy, C₁ -C₈ -alkylthio, phenoxy, benzyloxy, phenylthio,methoxycarbonylethyl or 5-membered or 6-membered hetaryl, and theseradicals may be monosubstituted to trisubstituted by halogen, nitro,phenoxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -haloalkyl, with theproviso that one or both of the substituents A and B is or are C₁ -C₈-alkoxy, C₁ -C₈ -alkylthio, phenoxy, benzyloxy, phenylthio or 5-memberedor 6-membered hetaryl,

D is halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, phenylthio or phenoxy,and these radicals may be monosubstituted to trisubstituted by halogen,nitro, phenoxy, C₁ -C₄ -alkyl or C₁ -C₄ -haloalkyl, and X is CH or N,and their plant-tolerated acid addition salts and metal complexes have abetter fungicidal action than known azole compounds.

The substituents in formula I have, for example, the following specificmeanings: A and B independently of one another are each straight-chainor branched C₁ -C₈ -alkyl, in particular C₁ -C₄ -alkyl, such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, C₃-C₆ -cycloalkyl, such as cyclopropyl, cyclopentyl or cyclohexyl, benzyl,phenyl, naphthyl, such as 1-naphthyl or 2-naphthyl, biphenyl, such aso-, m- or p-biphenyl, straight-chain or branched C₁ -C₈ -alkoxy, inparticular C₁ -C₄ -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy or tert-butoxy, straight-chain or branched C₁ -C₈-alkylthio, in particular C₁ -C₄ -alkylthio, such as methylthio,ethylthio, propylthio, isopropylthio, butylthio, isobutylthio orsecbutylthio, benzyloxy, phenoxy, phenylthio, methoxycarbonylethyl or5-membered or 6-membered hetaryl, such as pyrrolyl, pyrrol-2-yl,pyrrol-3-yl, furan-2-yl, thien-2-yl, thien-3-yl, pyrid-2-yl, pyrid-3-yl,pyrid-4-yl, 1,3-diazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazolyl,isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-4-yl, thiazol-5-yl, imidazol-4-yl or 1,3-dioxolan-2-yl.

The stated radicals may be monosubstituted to trisubstituted by halogen,such as fluorine, chlorine or bromine, nitro, phenoxy, C₁ -C₄ -alkyl asstated specifically above, C₁ -C₄ -haloalkyl having from 1 to 3 halogenatoms, such as fluorine, chlorine or bromine, e.g. trifluoromethyl,chloroethyl or bromobutyl. D is halogen, such as chlorine or bromine,straight-chain or branched C₁ -C₄ -alkoxy as stated specifically above,straight-chain or branched C₁ -C₄ -alkylthio, as stated specificallyabove, phenoxy or phenylthio.

The stated radicals may be monosubstituted to trisubstituted by halogen,such as fluorine, chlorine or bromine, nitro, phenoxy, C₁ -C₄ -alkyl,e.g. methyl or ethyl, C₁ -C₄ -alkoxy as stated specifically above or C₁-C₄ -haloalkyl having from 1 to 3 halogen atoms, such as fluorine,chlorine or bromine, e.g. trifluoromethyl.

The compounds of the formula I contain asymmetric carbon atoms and cantherefore occur as enantiomers and diastereomers. The invention relatesboth to the pure isomers and to mixtures thereof. The mixtures ofdiastereomers can be separated into the components by known methods, forexample by fractional crystallization or by chromatography over silicagel. The racemates of the novel compounds can be separated byconventional methods, for example by salt formation with an opticallyactive acid, separation of the diastereomeric salts and liberation ofthe enantiomers by means of a base.

The individual diastereomers and mixtures thereof can be used asfungicidal active ingredients.

Acid addition salts are, for example, the hydrochlorides, bromides,sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates.The activity of the salts is due to the cation, so that the anion isgenerally unimportant. The acid addition salts are prepared by reactingthe azolylethane derivatives (I) with acids.

Metal complexes of the active ingredients I or of their salts can beformed with, for example, copper, zinc, tin, manganese, iron, cobalt ornickel by reacting the azolylethane derivatives with metal salts.

The novel compounds I in which D is chlorine or bromine are veryadvantageously prepared, for example, similarly to the method describedby H. Matsumoto et al. (Tetrahedron Lett. 52 (1979), 5011) by reactingan aldehyde of the formula II with an azole of the formula III and anacid halide (Y Hal₂) in accordance with the following empiricalequation: ##STR3##

The inorganic acid halides (Y Hal₂) are halogenating agents, such asphosphorus oxychloride, thiophosgene, preferably phosgene, thionylchloride and thionyl bromide.

The starting compounds II are known or are obtainable in a known manner(cf. H. Siegel, W. Himmele, Angew. Chem. 92 (1980), 182-187).

The acid halide is preferably used in not less than an equimolar amount,based on the aldehyde II. The azole component III is used, for example,in twice, preferably 5-6, times the molar amount, based on the acidchloride or bromide.

The reaction is preferably carried out at from -30° to +100° C.,particularly preferably from 0° to 20° C., in the presence of a solvent.

Examples of preferred solvents are nitriles, such as acetonitrile andethers, such as tetrahydrofuran, diethyl ether or dioxane. Hydrocarbonsand chlorohydrocarbons, such as hexane, benzene, toluene, methylenechloride or carbon tetrachloride, or mixtures of the stated solvents areparticularly preferred.

In general, the reaction is carried out at atmospheric pressure, unlessa higher pressure, for example up to 5 bar, is advisable owing toreadily volatile reactants.

Since the acid halides and the intermediates are sensitive tohydrolysis, the reaction is preferably carried out in the absence ofmoisture, particularly preferably in a protective gas atmosphere.

The novel compounds I in which D is C₁ -C₄ -alkoxy are veryadvantageously prepared, for example, similarly to the method describedin DE 31 50 204, by reacting an acetal of the formula IV with aninorganic or organic acid chloride R¹ -COCl and then with an azole ofthe formula III in accordance with the following empirical equation:##STR4##

The starting compounds IV are known or are obtainable in a known mannerby acetalization of the aldehydes II.

Suitable inorganic or organic acid halides are, for example, thionylchloride, thionyl bromide, acetyl chloride and acetyl bromide. Allconventional acid halides can also be used. The acid halide ispreferably employed in an equimolar amount, based on the acetal IV. Theazole component III is used in, for example, twice, preferably 4-6,times the molar amount, based on the acid halide.

The reaction is carried out at from -30° to +100° C., particularlypreferably from 0° to 30° C., in the presence of a solvent.

Examples of preferred solvents are ketones, such as acetone, methylethyl ketone or cyclohexanone, nitriles, such as acetonitrile orpropionitrile, alcohols, such as methanol, ethanol, isopropanol,n-butanol or glycols, esters, such as methyl acetate, ethyl acetate orbutyl acetate, ethers, such as tetrahydrofuran, diethyl ether,dimethoxyethane, dioxane or diisopropyl ether, amides, such asdimethylformamide, dimethylacetamide or N-methylpyrrolidone, anddimethyl sulfoxide, sulfolane and mixtures of the stated solvents.

Since the acid halides and the intermediates are sensitive tohydrolysis, the reaction is preferably carried out in the absence ofmoisture, particularly preferably in a protective gas atmosphere.

The compounds I in which D is a substituent other than chlorine, bromineor C₁ -C₄ -alkoxy can be particularly advantageously prepared from thechlorine or bromine compounds Ia by reacting these with a compound H-Dand a base. ##STR5##

The component H-D is advantageously used in a stoichiometric amount,preferably in about 20% excess, based on the azolylethane derivative Ia.

The reaction is advantageously carried out with the addition of anorganic or inorganic auxiliary base and/or of a reaction accelerator, inthe presence of a solvent.

The amount of base and reaction accelerator may be varied depending onthe compound used. Advantageously, a small excess of base, based on theazolylethane derivative Ia, is used.

Examples of suitable bases are alkali metal hydroxides, such as lithiumhydroxide, sodium hydroxide or potassium hydroxide, alkali metalcarbonates, such as sodium carbonate, potassium carbonate, sodiumbicarbonate or potassium bicarbonate, alkali metal amides, such assodium amide or potassium amide, and the organic bases pyridine,4-dialkylaminopyridine, dialkylamines and dialkylanilines, or preferablythe alkali metal salt of component H-D.

The reaction accelerator is preferably added to the reaction mixture ina catalytic amount.

Examples of suitable reaction accelerators are metal halides, preferablysodium iodide or potassium iodide, quaternary ammonium salts, such astetraalkylammonium chloride, bromide or iodide, aryltrialkylammoniumhalides, such as benzyltriethylammonium chloride or bromide, and crownethers, such as 12-crown-4, 15-crown-5, benzo-15-crown-5,dibenzo-18-crown-6 or dicyclohexano-18-crown-6.

Preferably used solvents are ketones, such as acetone, methyl ethylketone or cyclohexanone, nitriles, such as acetonitrile orpropionitrile, alcohols, such as methanol, ethanol, isopropanol,n-butanol or glycols, esters, such as methyl acetate, ethyl acetate orbutyl acetate, ethers, such as tetrahydrofuran, diethyl ether,dimethoxyethane, dioxane or diisopropyl ether, amides, such asdimethylformamide, dimethylacetamide or N-methyl-pyrrolidone, anddimethyl sulfoxide, sulfolane or mixtures of the stated solvents.

The reaction is advantageously carried out at from 0° to 180° C.,preferably at the boiling point of the solvent used.

The novel process for the preparation of azolylethane derivatives can becarried out continuously or batchwise.

The Examples which follow illustrate the preparation of the activeingredients.

PREPARATION EXAMPLES EXAMPLE 11-Chloro-1-(1,2,4-triazol-1-yl)-2-(4-methylphenoxy)-propane ##STR6##

23.5 g (0.2 mol) of thionyl chloride were added to a solution of 54.5 g(0.79 mol) of triazole in 150 ml of methylene chloride at 0° C. under anitrogen atmosphere, followed, after stirring for 30 minutes at 25° C.,by 20 g of 2-(4-methylphenoxy)-propanal.

After a reaction time of 12 hours at 25° C., 100 ml of water were added,after which the aqueous phase was separated off and extracted twice withmethylene chloride. The combined organic phases were then worked up in aconventional manner to obtain the triazole derivative.

Yield 25.5 g (84%).

EXAMPLE 21-Phenylthio-1-(1,2,4-triazol-1-yl)-2-(4-methylphenoxy)-propane ##STR7##

13 q (0.12 mol of thiophenol were added slowly at 25° C. to a solutionof 4.0 g of sodium hydride (80% strength by weight suspension in mineraloil) and 100 ml of N,N-dimethylformamide, followed, after stirring for30 minutes, by 19.8 g (0.08 mol) of1-chloro-1-(1,2,4-triazol-1-yl)-2-(4-methylphenoxy)-propane. After areaction time of 24 hours at 25° C., 100 ml of water were added.Extraction with methyl tert-butyl ether was carried out, after which theorganic phase was washed and was worked up in a conventional manner.

Yield: 18.7 g (72%).

The compounds shown in the Table were prepared similarly to Examples 1and 2.

                                      TABLE                                       __________________________________________________________________________     ##STR8##                                                                     Example                                                                            A        R.sup.1         D         X  m.p./IR[cm.sup.-1 ]                                                                        Isomer                __________________________________________________________________________     1   CH.sub.3                                                                                ##STR9##       Cl        N  1509, 1276, 1232, 1135,                                                                    D.sub.1 :D.sub.2                                                              = 2:1                  2   CH.sub.3                                                                                ##STR10##                                                                                     ##STR11##                                                                              N  resin        D.sub.1 :D.sub.2                                                              = 2:1                  3   CH.sub.3                                                                                ##STR12##      Cl        N                                      4   CH.sub.3                                                                                ##STR13##      Br        N                                      5   CH.sub.3                                                                                ##STR14##                                                                                     ##STR15##                                                                              N                                      6   CH.sub.3                                                                                ##STR16##      OCH.sub.3 N                                      7   CH.sub.3                                                                                ##STR17##      OC.sub.2 H.sub.5                                                                        N                                      8   CH.sub.3                                                                                ##STR18##      SCH.sub.3 N                                      9   CH.sub.3                                                                                ##STR19##      Cl        N  resin        D.sub.1 :D.sub.2                                                              = 2:1                  10  CH.sub.3                                                                                ##STR20##      OCH.sub.3 N                                      11  CH.sub.3                                                                                ##STR21##      OC.sub.2 H.sub.5                                                                        N                                      12  CH.sub.3                                                                                ##STR22##                                                                                     ##STR23##                                                                              N  resin        D.sub.1 :D.sub.2                                                              = 2:1                  13  CH.sub.3                                                                                ##STR24##                                                                                     ##STR25##                                                                              N                                      14  CH.sub.3                                                                                ##STR26##                                                                                     ##STR27##                                                                              N                                      15  CH.sub.3                                                                                ##STR28##                                                                                     ##STR29##                                                                              N                                      16  CH.sub. 3                                                                               ##STR30##      Cl        N  1479, 1277, 1262, 1135,                                                                    D.sub.1 :D.sub.2                                                              = 3:2                  17  CH.sub.3                                                                                ##STR31##      OCH.sub.3 N                                      18  CH.sub.3                                                                                ##STR32##      OC.sub.2 H.sub.5                                                                        N                                      19  CH.sub.3                                                                                ##STR33##                                                                                     ##STR34##                                                                              N                                      20  CH.sub.3                                                                                ##STR35##                                                                                     ##STR36##                                                                              N                                      21  CH.sub.3                                                                                ##STR37##                                                                                     ##STR38##                                                                              N                                      22  CH.sub.3                                                                                ##STR39##                                                                                     ##STR40##                                                                              N                                      23  CH.sub.3                                                                                ##STR41##                                                                                     ##STR42##                                                                              N                                      24  CH.sub.3                                                                                ##STR43##                                                                                     ##STR44##                                                                              N                                      25  CH.sub.3                                                                                ##STR45##      Cl        N                                      26  CH.sub.3                                                                                ##STR46##      OCH.sub.3 N                                      27  CH.sub.3                                                                                ##STR47##                                                                                     ##STR48##                                                                              N                                      28  CH.sub.3                                                                                ##STR49##                                                                                     ##STR50##                                                                              N                                      29  CH.sub.3                                                                                ##STR51##                                                                                     ##STR52##                                                                              N                                      30  CH.sub.3                                                                                ##STR53##                                                                                     ##STR54##                                                                              N                                      31  CH.sub.3                                                                                ##STR55##                                                                                     ##STR56##                                                                              N                                      32  CH.sub.3                                                                                ##STR57##      Cl        N  resin        D.sub.1 :D.sub.2                                                              = 3:1                  33  CH.sub.3                                                                                ##STR58##      Cl        N  1505, 1276, 1136, 1100, 741,                                                  698          D.sub.1 :D.sub.2                                                              = 6:5                  34  CH.sub.3                                                                                ##STR59##      OCH.sub.3 N                                      35  CH.sub.3                                                                                ##STR60##      OC.sub.2 H.sub.5                                                                        N                                      36  CH.sub.3                                                                                ##STR61##      SCH.sub.3 N                                      37  CH.sub.3                                                                                ##STR62##                                                                                     ##STR63##                                                                              N                                      38  CH.sub.3                                                                                ##STR64##                                                                                     ##STR65##                                                                              N                                      39  CH.sub.3                                                                                ##STR66##                                                                                     ##STR67##                                                                              N                                      40  CH.sub.3                                                                                ##STR68##                                                                                     ##STR69##                                                                              N                                      41  CH.sub.3 OCH.sub.3       Cl        N                                      42  CH.sub.3 OCH.sub.3                                                                                      ##STR70##                                                                              N                                      43  CH.sub.3 OCH.sub.3                                                                                      ##STR71##                                                                              N                                      44  CH.sub.3 OCH.sub.3                                                                                      ##STR72##                                                                              N                                      45  CH.sub.3 OCH.sub.3                                                                                      ##STR73##                                                                              N                                      46  CH.sub.3 OCH.sub.3                                                                                      ##STR74##                                                                              N                                      47  CH.sub.3 OC.sub.2 H.sub.5                                                                              Cl        N                                      48  CH.sub.3 O.sub.2 CH.sub.5                                                                               ##STR75##                                                                              N                                      49  CH.sub.3 O.sub.2 CH.sub.5                                                                               ##STR76##                                                                              N                                      50  CH.sub.3 O.sub.2 CH.sub.5                                                                               ##STR77##                                                                              N                                      51  CH.sub.3 O.sub.2 CH.sub.5                                                                               ##STR78##                                                                              N                                      52  CH.sub.3 OC.sub.3 H.sub.7                                                                              Cl        N                                      53  CH.sub.3 OC.sub.3 H.sub.7                                                                               ##STR79##                                                                              N                                      54  CH.sub.3 OC.sub.3 H.sub.7                                                                               ##STR80##                                                                              N                                      55  CH.sub.3 OC.sub.3 H.sub.7                                                                               ##STR81##                                                                              N                                      56  CH.sub.3 OC.sub.3 H.sub.7                                                                               ##STR82##                                                                              N                                      57  CH.sub.3 OC.sub.4 H.sub.9                                                                              Cl        N                                      58  CH.sub.3 OC.sub.4 H.sub.9                                                                               ##STR83##                                                                              N                                      59  CH.sub.3 OC.sub.4 H.sub.9                                                                               ##STR84##                                                                              N                                      60  CH.sub.3 OC.sub.4 H.sub.9                                                                               ##STR85##                                                                              N                                      61  CH.sub.3 OC.sub.4 H.sub.9                                                                               ##STR86##                                                                              N                                      62  CH.sub.3 SCH.sub.3       Cl        N                                      63  CH.sub.3 SCH.sub.3                                                                                      ##STR87##                                                                              N                                      64  CH.sub.3 SCH.sub.3                                                                                      ##STR88##                                                                              N                                      65  CH.sub.3 SCH.sub.3                                                                                      ##STR89##                                                                              N                                      66  CH.sub.3 SC.sub.2 H.sub.5                                                                              Cl        N                                      67  CH.sub.3 SC.sub.2 H.sub.5                                                                               ##STR90##                                                                              N                                      68  CH.sub.3 SC.sub.2 H.sub.5                                                                               ##STR91##                                                                              N                                      69  CH.sub.3 SC.sub.2 H.sub.5                                                                               ##STR92##                                                                              N                                      70  CH.sub.3                                                                                ##STR93##      Cl        N                                      71  CH.sub.3                                                                                ##STR94##                                                                                     ##STR95##                                                                              N                                      72  CH.sub.3                                                                                ##STR96##                                                                                     ##STR97##                                                                              N                                      73  CH.sub.3                                                                                ##STR98##                                                                                     ##STR99##                                                                              N                                       74 CH.sub.3                                                                                ##STR100##                                                                                    ##STR101##                                                                             N                                      75  H        C.sub.6 H.sub.5 Cl        N                                      76  H        4-ClC.sub.6 H.sub.4                                                                           Cl        N                                      77  H        2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                  Cl        N                                      78  H        2-ClC.sub.6 H.sub.4                                                                           Cl        N                                      79  H        4-FC.sub.6 H.sub.4                                                                            Cl        N  resin                               80  H        4-FC.sub.6 H.sub.4                                                                             ##STR102##                                                                             N  1510, 1274, 1224, 1135, 748         81  H        4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                      82  H        2-Thienyl       Cl        N                                      83  H        3-Thienyl       Cl        N                                      84  H        2-Furyl         Cl        N                                      85  C.sub.2 H.sub.5                                                                        OC.sub.6 H.sub.5                                                                              Cl        N                                      86  C.sub.2 H.sub.5                                                                        O.sub.3 C.sub.6 H.sub.5                                                                       SC.sub.6 H.sub.5                                                                        N                                      87  C.sub.2 H.sub.5                                                                        OC.sub.6 H.sub.5                                                                               ##STR103##                                                                             N                                      88  C.sub.2 H.sub.5                                                                         ##STR104##     Cl        N                                      89  C.sub.2 H.sub.5                                                                         ##STR105##     SC.sub.6 H.sub.5                                                                        N                                      90  C.sub.2 H.sub.5                                                                         ##STR106##     Cl        N                                      91  C.sub.2 H.sub.5                                                                         ##STR107##     SC.sub.6 H.sub.5                                                                        N                                      92  CH.sub.3                                                                                ##STR108##                                                                                    ##STR109##                                                                             N                                      93  C.sub.2 H.sub.5                                                                         ##STR110##     Cl        N                                      94  C.sub.2 H.sub.5                                                                         ##STR111##     SC.sub.6 H.sub.5                                                                        N                                      95  C.sub.2 H.sub.5                                                                         ##STR112##                                                                                    ##STR113##                                                                             N                                      96  C.sub.2 H.sub.5                                                                         ##STR114##                                                                                    ##STR115##                                                                             N                                      97  C.sub.2 H.sub.5                                                                         ##STR116##     Cl        N                                      98  C.sub.2 H.sub.5                                                                         ##STR117##                                                                                    ##STR118##                                                                             N                                      99  C.sub.2 H.sub.5                                                                         ##STR119##                                                                                    ##STR120##                                                                             N                                     100  C.sub.2 H.sub.5                                                                         ##STR121##                                                                                    ##STR122##                                                                             N                                     101  C.sub.2 H.sub.5                                                                        OCH.sub.2 C.sub.6 H.sub.5                                                                     Cl        N                                     102  C.sub.2 H.sub.5                                                                        OCH.sub.3       Cl        N                                     103  C.sub.2 H.sub.5                                                                        OCH.sub.3                                                                                      ##STR123##                                                                             N                                     104  C.sub.2 H.sub.5                                                                        OCH.sub.3                                                                                      ##STR124##                                                                             N                                     105  C.sub.2 H.sub.5                                                                        OCH.sub.3       SC.sub.6 H.sub.5                                                                        N                                     106  C.sub.2 H.sub.5                                                                        OC.sub.2 H.sub.5                                                                              Cl        N                                     107  C.sub.2 H.sub.5                                                                        OC.sub.3 H.sub.7                                                                              Cl        N                                     108  C.sub.2 H.sub.5                                                                        SCH.sub.3       Cl        N                                     109  C.sub.2 H.sub.5                                                                        SC.sub.2 H.sub.5                                                                              Cl        N                                     110  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                              Cl        N                                     111  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                              OC.sub.6 H.sub.5                                                                        N                                     112  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                               ##STR125##                                                                             N                                     113  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                               ##STR126##                                                                             N                                     114  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                               ##STR127##                                                                             N                                     115  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                              SC.sub.6 H.sub.5                                                                        N                                     116  C.sub.2 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                               ##STR128##                                                                             N                                     117  C.sub.3 H.sub.7                                                                        OC.sub.6 H.sub.5                                                                              Cl        N                                     118  C.sub.3 H.sub.7                                                                        OC.sub.6 H.sub.5                                                                              SC.sub.6 H.sub.5                                                                        N                                     119  C.sub.3 H.sub.7                                                                        OC.sub.6 H.sub.5                                                                               ##STR129##                                                                             N                                     120  C.sub.3 H.sub.7                                                                         ##STR130##     Cl        N                                     121  C.sub.3 H.sub.7                                                                         ##STR131##     SC.sub.6 H.sub.5                                                                        N                                     122  C.sub.3 H.sub.7                                                                         ##STR132##                                                                                    ##STR133##                                                                             N                                     123  C.sub.3 H.sub.7                                                                         ##STR134##     Cl        N                                     124  C.sub.3 H.sub.7                                                                         ##STR135##     SC.sub.6 H.sub.5                                                                        N                                     125  C.sub.3 H.sub.7                                                                         ##STR136##                                                                                    ##STR137##                                                                             N                                     126  C.sub.3 H.sub.7                                                                         ##STR138##     Cl        N                                     127  C.sub.3 H.sub.7                                                                         ##STR139##                                                                                    ##STR140##                                                                             N                                     128  C.sub.3 H.sub.7                                                                         ##STR141##                                                                                    ##STR142##                                                                             N                                     129  C.sub.3 H.sub.7                                                                         ##STR143##     Cl        N                                     130  C.sub.3 H.sub.7                                                                         ##STR144##                                                                                    ##STR145##                                                                             N                                     121  C.sub.3 H.sub.7                                                                         ##STR146##                                                                                    ##STR147##                                                                             N                                     132  C.sub.3 H.sub.7                                                                        OCH.sub.2 C.sub.6 H.sub.5                                                                     Cl        N                                     133  C.sub.3 H.sub.7                                                                        OCH.sub.3       Cl        N                                     134  C.sub.3 H.sub.7                                                                        OCH.sub.3                                                                                      ##STR148##                                                                             N                                     135  C.sub.3 H.sub.7                                                                        OCH.sub.3                                                                                      ##STR149##                                                                             N                                     136  C.sub.3 H.sub.7                                                                        OCH.sub.3       SC.sub.6 H.sub.5                                                                        N                                     137  C.sub.3 H.sub.7                                                                        OC.sub.2 H.sub.5                                                                              Cl        N                                     138  C.sub.3 H.sub.7                                                                        OC.sub.3 H.sub.7                                                                              Cl        N                                     139  C.sub.3 H.sub.7                                                                        SCH.sub.3       Cl        N                                     140  C.sub. 3 H.sub.7                                                                       SC.sub.2 H.sub.5                                                                              Cl        N                                     141  C.sub.3 H.sub.7                                                                        SC.sub.2 H.sub.5                                                                              OC.sub.6 H.sub.5                                                                        N                                     142  C.sub.3 H.sub.7                                                                        SC.sub.2 H.sub.5                                                                               ##STR150##                                                                             N                                     143  C.sub.3 H.sub.7                                                                        SC.sub.2 H.sub.5                                                                               ##STR151##                                                                             N                                     144  C.sub.3 H.sub.7                                                                        SC.sub.2 H.sub.5                                                                               ##STR152##                                                                             N                                     145  C.sub.3 H.sub.7                                                                        SC.sub.2 H.sub.5                                                                              SC.sub.6 H.sub.5                                                                        N                                     146  C.sub.3 H.sub.7                                                                        SC.sub.2 H.sub.5                                                                               ##STR153##                                                                             N                                     147  C.sub.3 H.sub.7                                                                        SC.sub.6 H.sub.5                                                                              Cl        N                                     148  C.sub.3 H.sub.7                                                                        SC.sub.6 H.sub.5                                                                              OC.sub.6 H.sub.5                                                                        N                                     149  C.sub.3 H.sub.7                                                                        SC.sub.6 H.sub.5                                                                               ##STR154##                                                                             N                                     150  C.sub.3 H.sub.7                                                                        SC.sub.6 H.sub.5                                                                               ##STR155##                                                                             N                                     151  C.sub.3 H.sub.7                                                                        SC.sub.6 H.sub.5                                                                               ##STR156##                                                                             N                                     152  C.sub.3 H.sub.7                                                                        SC.sub.6 H.sub.5                                                                              SC.sub.6 H.sub.5                                                                        N                                     153  C.sub.4 H.sub.9                                                                        OC.sub.6 H.sub.5                                                                              Cl        N                                     154  C.sub.4 H.sub.9                                                                         ##STR157##     Cl        N                                     155  C.sub.4 H.sub.9                                                                         ##STR158##     Cl        N                                     156  C.sub.4 H.sub.9                                                                         ##STR159##     Cl        N                                     157  C.sub.4 H.sub.9                                                                         ##STR160##     Cl        N                                     158  C.sub.4 H.sub.9                                                                        OCH.sub.2 C.sub.6 H.sub.5                                                                     Cl        N                                     159  C.sub.4 H.sub.9                                                                        OCH.sub.3       Cl        N                                     160  C.sub.4 H.sub.9                                                                        OC.sub.3 H.sub.7                                                                              Cl        N                                     161  C.sub.4 H.sub.9                                                                        SCH.sub.3       Cl        N                                     162  C.sub.4 H.sub.9                                                                        SC.sub.6 H.sub.5                                                                              Cl        N                                     163  C.sub.6 H.sub.5                                                                        OC.sub.6 H.sub.5                                                                              Cl        N                                     164  C.sub.6 H.sub.5                                                                         ##STR161##     Cl        N                                     165  C.sub.6 H.sub.5                                                                         ##STR162##     Cl        N                                     166  C.sub.6 H.sub.5                                                                         ##STR163##     Cl        N                                     167  C.sub.6 H.sub.5                                                                         ##STR164##     Cl        N                                     168  C.sub.6 H.sub.5                                                                        OCH.sub.3       Cl        N                                     169  C.sub.6 H.sub.5                                                                        SCH.sub.3       Cl        N                                     170  C.sub.6 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                              Cl        N                                     171  4-FC.sub.6 H.sub.4                                                                     OC.sub.6 H.sub.5                                                                              Cl        N                                     172  4-FC.sub.6 H.sub.4                                                                      ##STR165##     Cl        N                                     173  4-FC.sub.6 H.sub.4                                                                      ##STR166##     Cl        N                                     174  4-FC.sub.6 H.sub.4                                                                      ##STR167##     Cl        N                                     175  4-FC.sub.6 H.sub.4                                                                      ##STR168##     Cl        N                                     176  4-FC.sub.6 H.sub.4                                                                     OCH.sub.3       Cl        N                                     177  4-FC.sub.6 H.sub.4                                                                     SCH.sub. 3      Cl        N                                     178  4-FC.sub.6 H.sub.4                                                                     SC.sub.6 H.sub.5                                                                              Cl        N                                     179  2-FC.sub.6 H.sub.4                                                                     OC.sub.6 H.sub.5                                                                              Cl        N                                     180  2-FC.sub.6 H.sub.4                                                                     OCH.sub.3       Cl        N                                     181  2-FC.sub.6 H.sub.4                                                                     SC.sub.6 H.sub.5                                                                              Cl        N                                     182  4-ClC.sub.6 H.sub.4                                                                    OC.sub.6 H.sub.5                                                                              Cl        N                                     183  4-ClC.sub.6 H.sub.4                                                                     ##STR169##     Cl        N                                     184  4-ClC.sub.6 H.sub.4                                                                     ##STR170##     Cl        N                                     185  4-ClC.sub.6 H.sub.4                                                                     ##STR171##     Cl        N                                     186  4-ClC.sub.6 H.sub.4                                                                     ##STR172##     Cl        N                                     187  4-ClC.sub.6 H.sub.4                                                                    OCH.sub.3       Cl        N                                     188  4-ClC.sub.6 H.sub.4                                                                    SCH.sub.3       Cl        N                                     189  4-ClC.sub.6 H.sub.4                                                                    SC.sub.6 H.sub.5                                                                              Cl        N                                     190  2-ClC.sub.6 H.sub.4                                                                    OC.sub.6 H.sub.5                                                                              Cl        N                                     191  2-ClC.sub.6 H.sub.4                                                                    OCH.sub.3       Cl        N                                     192  2-ClC.sub.6 H.sub. 4                                                                   SC.sub.6 H.sub.5                                                                              Cl        N                                     193  2,4-Cl.sub.2 C.sub.6 H.sub.3                                                           OC.sub.6 H.sub.5                                                                              Cl        N                                     194  2,4-Cl.sub.2 C.sub.6 H.sub.3                                                           OCH.sub.3       Cl        N                                     195  2,4-Cl.sub.2 C.sub.6 H.sub.3                                                           SC.sub.6 H.sub.5                                                                              Cl        N                                     196  4-BrC.sub.6 H.sub.4                                                                    OCH.sub.3       Cl        N                                     197  4-CH.sub.3 C.sub.6 H.sub.4                                                             OC.sub.6 H.sub.5                                                                              Cl        N                                     198  4-CH.sub.3 C.sub.6 H.sub.4                                                             OCH.sub.3       Cl        N                                     199  4-CH.sub.3 C.sub.6 H.sub.4                                                             SC.sub.6 H.sub.5                                                                              Cl        N                                     200  4-OCH.sub.3 C.sub.6 H.sub.4                                                            OC.sub.6 H.sub.5                                                                              Cl        N                                     201  4-OCH.sub.3 C.sub.6 H.sub.4                                                            OCH.sub.3       Cl        N                                     202  4-OCH.sub.3 C.sub.6 H.sub.4                                                            SC.sub.6 H.sub.5                                                                              Cl        N                                     203  4-CF.sub.3 C.sub.6 H.sub.4                                                             OC.sub.6 H.sub.5                                                                              Cl        N                                     204  4-CF.sub.3 C.sub.6 H.sub.4                                                             OCH.sub.3       Cl        N                                     205  4-CF.sub.3 C.sub.6 H.sub.4                                                             SC.sub.6 H.sub.5                                                                              Cl        N                                     206  4-Biphenyl                                                                             OC.sub.6 H.sub.5                                                                              Cl        N                                     207  4-Biphenyl                                                                             OCH.sub.3       Cl        N                                     208  4-Biphenyl                                                                             SC.sub.6 H.sub.5                                                                              Cl        N                                     209  1-Naphthyl                                                                             OCH.sub.3       Cl        N                                     210  2-Naphthyl                                                                             OC.sub.6 H.sub.5                                                                              Cl        N                                     211  2-Naphthyl                                                                             OCH.sub.3       Cl        N                                     212  2-Naphthyl                                                                             SC.sub.6 H.sub.5                                                                              Cl        N                                     213  Cyclopentyl                                                                            OC.sub.6 H.sub.5                                                                              Cl        N                                     214  Cyclopentyl                                                                             ##STR173##     Cl        N                                     215  Cyclopentyl                                                                            OCH.sub.3       Cl        N                                     216  Cyclopentyl                                                                            SC.sub.6 H.sub.5                                                                              Cl        N                                     217  Cyclohexyl                                                                             OC.sub.6 H.sub.5                                                                              Cl        N                                     218  Cyclohexyl                                                                              ##STR174##     Cl        N                                     219  Cyclohexyl                                                                             OCH.sub.3       Cl        N                                     220  Cyclohexyl                                                                             SC.sub.6 H.sub.5                                                                              Cl        N                                     221  2-Thienyl                                                                              CH.sub.3        Cl        N                                     222  2-Thienyl                                                                              CH.sub.3                                                                                       ##STR175##                                                                             N                                     223  2-Thienyl                                                                              C.sub.2 H.sub.5 Cl        N                                     224  2-Thienyl                                                                              C.sub.2 H.sub.5                                                                                ##STR176##                                                                             N                                     225  2-Thienyl                                                                              C.sub.3 H.sub.7 Cl        N  2960, 1506, 1275, 1135,                                                                    D.sub.1 :D.sub.2                                                              = 3:2                 226  2-Thienyl                                                                              C.sub.3 H.sub.7 Cl        CH 2959, 1489, 1226, 1078,                                                                    D.sub.1 :D.sub.2                                                              =  2:1                227  2-Thienyl                                                                              C.sub.3 H.sub.7 OCH.sub.3 N                                     228  2-Thienyl                                                                              C.sub.3 H.sub.7                                                                                ##STR177##                                                                             N                                     229  2-Thienyl                                                                              C.sub.3 H.sub.7 SC.sub.6 H.sub.5                                                                        N                                     230  2-Thienyl                                                                              C.sub.3 H.sub.7                                                                                ##STR178##                                                                             N                                     231  2-Thienyl                                                                              C.sub.6 H.sub.5 Cl        N                                     232  2-Thienyl                                                                              4-ClC.sub.6 H.sub.4                                                                           Cl        N                                     233  2-Thienyl                                                                              2-ClC.sub.6 H.sub.4                                                                           Cl        N                                     234  2-Thienyl                                                                              2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                  Cl        N                                     235  2-Thienyl                                                                              4-FC.sub.6 H.sub.4                                                                            Cl        N                                     236  2-Thienyl                                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                     237  2-Thienyl                                                                              4-OCH.sub.3 C.sub.6 H.sub.4                                                                   Cl        N                                     238  2-Thienyl                                                                              4-Biphenyl      Cl        N                                     239  2-Thienyl                                                                              1-Naphthyl      Cl        N                                     240  2-Thienyl                                                                              2-Naphthyl      Cl        N                                     241  2-Thienyl                                                                              CH.sub.2 C.sub.6 H.sub.5                                                                      Cl        N                                     242  2-Thienyl                                                                              Cyclopentyl     Cl        N                                     243  2-Thienyl                                                                              Cyclohexyl      Cl        N                                     244  3-Thienyl                                                                              CH.sub.3        Cl        N                                     245  3-Thienyl                                                                              CH.sub.3                                                                                       ##STR179##                                                                             N                                     246  3-Thienyl                                                                              C.sub.2 H.sub.5 Cl        N  2970, 1506, 1275,                                                                          D.sub.1 :D.sub.2                                                              = 2:1                                                            778, 702                           247  3-Thienyl                                                                              C.sub.2 H.sub.5 Cl        CH 86-88° C.                                                                           D.sub.1 :D.sub.2                                                              = 2:1                 248  3-Thienyl                                                                              C.sub.2 H.sub.5 OCH.sub.3 N                                     249  3-Thienyl                                                                              C.sub.2 H.sub.5                                                                                ##STR180##                                                                             N                                     250  3-Thienyl                                                                              C.sub.2 H.sub.5                                                                                ##STR181##                                                                             N                                     251  3-Thienyl                                                                              C.sub.2 H.sub.5 SC.sub.6 H.sub.5                                                                        N  1502, 1439, 1274,                                                                          D.sub.1 :D.sub.2                                                              = 2:1                                                            1011, 702                          252  3-Thienyl                                                                              C.sub.2 H.sub.5 SC.sub.6 H.sub.5                                                                        CH 1501, 1476, 1274,                                                                          D.sub.1 :D.sub.2                                                              = 2:1                                                            1095, 1013                         253  3-Thienyl                                                                              C.sub.2 H.sub.5                                                                                ##STR182##                                                                             N                                     254  3-Thienyl                                                                              C.sub.3 H.sub.7 Cl        N                                     255  3-Thienyl                                                                              C.sub.3 H.sub.7 OCH.sub.3 N                                     256  3-Thienyl                                                                              C.sub.3 H.sub.7                                                                                ##STR183##                                                                             N                                     257  3-Thienyl                                                                              C.sub.3 H.sub.7 SC.sub.6 H.sub. 5                                                                       N                                     258  3-Thienyl                                                                              C.sub.3 H.sub.7                                                                                ##STR184##                                                                             N                                     259  3-Thienyl                                                                              C.sub.6 H.sub.5 Cl        N                                     260  3-Thienyl                                                                              4-ClC.sub.6 H.sub.4                                                                           Cl        N                                     261  3-Thienyl                                                                              2-ClC.sub.6 H.sub.4                                                                           Cl        N                                     262  3-Thienyl                                                                              2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                  Cl        N                                     263  3-Thienyl                                                                              4-FC.sub.6 H.sub.4                                                                            Cl        N                                     264  3-Thienyl                                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                     265  3-Thienyl                                                                              4-OCH.sub.3 C.sub.6 H.sub.4                                                                   Cl        N                                     266  2-Furyl  CH.sub.3        Cl        N                                     267  2-Furyl  C.sub.2 H.sub.5 Cl        N                                     268  2-Furyl  C.sub.2 H.sub.5 Cl        CH                                    269  2-Furyl  C.sub.2 H.sub.5 OCH.sub.3 N                                     270  2-Furyl  C.sub.3 H.sub.7 Cl        N                                     271  2-Furyl  C.sub.3 H.sub.7 OCH.sub.3 N                                     272  2-Furyl  C.sub.3 H.sub.7                                                                                ##STR185##                                                                             N                                     273  2-Furyl  C.sub.3 H.sub.7 SC.sub.6 H.sub.5                                                                        N                                     274  2-Furyl  C.sub.6 H.sub.1.sup.3                                                                         Cl        N  2927, 1489, 1227,                                                                          D.sub.1 :D.sub.2                                                              = 1:1                                                            1076, 733                          275  2-Furyl  C.sub.6 H.sub. 1.sup.3                                                                        Cl        CH 2928, 1505, 1275,                                                                          D.sub.1 :D.sub.2                                                              = 2:1                                                            1011, 734                          276  2-Furyl  C.sub.6 H.sub.1.sup.3                                                                         OCH.sub.3 N                                     277  2-Furyl  C.sub.6 H.sub.1.sup.3                                                                          ##STR186##                                                                             N                                     278  2-Furyl  C.sub.6 H.sub.1.sup.3                                                                         SC.sub.6 H.sub.5                                                                        N                                     279  2-Furyl  C.sub.6 H.sub.5 Cl        N                                     280  2-Furyl  4-ClC.sub.6 H.sub.4                                                                           Cl        N                                     281  2-Furyl  2-ClC.sub.6 H.sub.4                                                                           Cl        N                                     282  2-Furyl  4-FC.sub.6 H.sub.4                                                                            Cl        N                                     283  2-Furyl  2-FC.sub.6 H.sub.4                                                                            Cl        N                                     284  2-Furyl  4-BrC.sub.6 H.sub.4                                                                           Cl        N                                     285  2-Furyl  4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                     286  2-Furyl  4-OCH.sub.3 C.sub.6 H.sub.4                                                                   Cl        N                                     287  2-Pyridyl                                                                              CH.sub.3        Cl        N                                     288  2-Pyridyl                                                                              C.sub.2 H.sub.5 Cl        N                                     289  2-Pyridyl                                                                              C.sub.2 H.sub.5 Cl        CH                                    290  2-Pyridyl                                                                              C.sub.2 H.sub.5 OCH.sub.3 N                                     291  2-Pyridyl                                                                              C.sub.2 H.sub.5                                                                                ##STR187##                                                                             N                                     292  2-Pyridyl                                                                              C.sub.3 H.sub.7 Cl        N                                     293  2-Pyridyl                                                                              C.sub.3 H.sub.7 Cl        CH                                    294  2-Pyridyl                                                                              C.sub.3 H.sub.7 OCH.sub.3 N                                     295  2-Pyridyl                                                                              C.sub.3 H.sub.7                                                                                ##STR188##                                                                             N                                     296  2-Pyridyl                                                                              C.sub.6 H.sub.5 Cl        N                                     297  2-Pyridyl                                                                              4-ClC.sub.6 H.sub.4                                                                           Cl        N                                     298  2-Pyridyl                                                                              2-ClC.sub.6 H.sub.4                                                                           Cl        N                                     299  2-Pyridyl                                                                              2-FC.sub.6 H.sub.4                                                                            Cl        N                                     300  2-Pyridyl                                                                              4-FC.sub.6 H.sub.4                                                                            Cl        N                                     301  2-Pyridyl                                                                              4-BrC.sub.6 H.sub.4                                                                           Cl        N                                     302  2-Pyridyl                                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                     303  2-Pyridyl                                                                              4-OCH.sub.3 C.sub.6 H.sub.4                                                                   Cl        N                                     304  3-Pyridyl                                                                              CH.sub.3        Cl        N                                     305  3-Pyridyl                                                                              CH.sub.3        Cl        N                                     306  3-Pyridyl                                                                              C.sub.2 H.sub.5 Cl        N                                     307  3-Pyridyl                                                                              C.sub.2 H.sub.5 Cl        CH                                    308  3-Pyridyl                                                                              C.sub.2 H.sub.5 OCH.sub.3 N                                     309  3-Pyridyl                                                                              C.sub.2 H.sub.5                                                                                ##STR189##                                                                             N                                     310  3-Pyridyl                                                                              C.sub.2 H.sub.5 SC.sub.6 H.sub.5                                                                        N                                     311  3-Pyridyl                                                                              C.sub.3 H.sub.7 Cl        N                                     312  3-Pyridyl                                                                              C.sub.3 H.sub.7 Cl        CH                                    313  3-Pyridyl                                                                              C.sub.3 H.sub.7 OCH.sub.3 N                                     314  3-Pyridyl                                                                              C.sub.3 H.sub.7                                                                                ##STR190##                                                                             N                                     315  3-Pyridyl                                                                              C.sub.3 H.sub.7                                                                                ##STR191##                                                                             N                                     316  3-Pyridyl                                                                              C.sub.6 H.sub.5 Cl        N                                     317  3-Pyridyl                                                                              4-ClC.sub.6 H.sub.4                                                                           Cl        N                                     318  3-Pyridyl                                                                              2-ClC.sub.6 H.sub.4                                                                           Cl        N                                     319  3-Pyridyl                                                                              4-FC.sub.6 H.sub.4                                                                            Cl        N                                     320  3-Pyridyl                                                                              2-FC.sub.6 H.sub.4                                                                            Cl        N                                     321  3-Pyridyl                                                                              4-BrC.sub.6 H.sub.4                                                                           Cl        N                                     322  3-Pyridyl                                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                     323  3-Pyridyl                                                                              4-OCH.sub.3 C.sub.6 H.sub.4                                                                   Cl        N                                     324  4-Pyridyl                                                                              CH.sub.3        Cl        N                                     325  4-Pyridyl                                                                              CH.sub.3        Cl        CH                                    326  4-Pyridyl                                                                              C.sub.2 H.sub.5 Cl        N                                     327  4-Pyridyl                                                                              C.sub.2 H.sub.5 Cl        CH                                    328  4-Pyridyl                                                                              C.sub.2 H.sub.5 OCH.sub.3 N                                     329  4-Pyridyl                                                                              C.sub.2 H.sub.5                                                                                ##STR192##                                                                             N                                     330  4-Pyridyl                                                                              C.sub.2 H.sub.5 SC.sub.6 H.sub.5                                                                        N                                     331  4-Pyridyl                                                                              C.sub.3 H.sub.7 Cl        N                                     332  4-Pyridyl                                                                              C.sub.3 H.sub.7 Cl        CH                                    333  4-Pyridyl                                                                              C.sub.3 H.sub.7 OCH.sub.3 N                                     334  4-Pyridyl                                                                              C.sub.3 H.sub.7                                                                                ##STR193##                                                                             N                                     335  4-Pyridyl                                                                              C.sub.3 H.sub.7 SC.sub.6 H.sub.5                                                                        N                                     336  4-Pyridyl                                                                              C.sub.6 H.sub.5 Cl        N                                     337  4-Pyridyl                                                                              4-ClC.sub.6 H.sub.4                                                                           Cl        N                                     338  4-Pyridyl                                                                              2-ClC.sub.6 H.sub.4                                                                           Cl        N                                     339  4-Pyridyl                                                                              4-FC.sub.6 H.sub.4                                                                            Cl        N                                     340  4-Pyridyl                                                                              2-FC.sub.6 H.sub.4                                                                            Cl        N                                     341  4-Pyridyl                                                                              4-BrC.sub.6 H.sub.4                                                                           Cl        N                                     342  4-Pyridyl                                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                                    Cl        N                                     343  4-Pyridyl                                                                              4-OCH.sub.3 C.sub.6 H.sub.4                                                                   Cl        N                                     344  4-Oxazolyl                                                                             CH.sub.3        Cl        N                                     345  4-Oxazolyl                                                                             C.sub.2 H.sub.5 Cl        N                                     346  5-Oxazolyl                                                                             CH.sub.3        Cl        N                                     347  5-Oxazolyl                                                                             C.sub.2 H.sub.5 Cl        N                                     348  5-Oxazolyl                                                                             C.sub.6 H.sub.5 Cl        N                                     349  3-Isoxazolyl                                                                           CH.sub.3        Cl        N                                     350  3-Isoxazolyl                                                                           C.sub.2 H.sub.5 Cl        N                                     351  3-Isoxazolyl                                                                           C.sub.6 H.sub.5 Cl        N                                     352  4-Isoxazolyl                                                                           CH.sub.3        Cl        N                                     353  4-Isoxazolyl                                                                           C.sub.2 H.sub.5 Cl        N                                     354  4-Isoxazolyl                                                                           C.sub.6 H.sub.5 Cl        N                                     355  5-Isoxazolyl                                                                           CH.sub.3        Cl        N                                     356  5-Isoxazolyl                                                                           C.sub.2 H.sub.5 Cl        N                                     357  5-Isoxazolyl                                                                           C.sub.6 H.sub.5 Cl        N                                     358  4-Thiazolyl                                                                            CH.sub.3        Cl        N                                     359  4-Thiazolyl                                                                            C.sub.2 H.sub.5 Cl        N                                     360  4-Thiazolyl                                                                            C.sub.6 H.sub.5 Cl        N                                     361  5-Thiazolyl                                                                            CH.sub.3        Cl        N                                     362  5-Thiazolyl                                                                            C.sub.2 H.sub.5 Cl        N                                     363  5-Thiazolyl                                                                            C.sub.6 H.sub.5 Cl        N                                     364                                                                                 ##STR194##                                                                            CH.sub.3        Cl        N                                     365                                                                                 ##STR195##                                                                            C.sub.6 H.sub.5 Cl        N                                     366  CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                    C.sub.6 H.sub.5 Cl        N  1729, 1506, 1276,                                                                          D.sub.1 :D.sub.2                                                              = 3:1                                                            1135, 702 cm-1                     367  CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                    C.sub.6 H.sub.5 Cl        CH                                    368  CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                    C.sub.6 H.sub.5 OCH.sub.3 N                                     369  CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                    C.sub.6 H.sub.5 SC.sub.6 H.sub.5                                                                        N                                     370  CH.sub.3                                                                                ##STR196##     Cl        N  resin        D.sub.1 :D.sub. 2                                                             = 3:1                 __________________________________________________________________________     D.sub.1 :D.sub.2 = ratio of the diastereomers formed                     

In general terms, the novel compounds are extremely effective on a broadspectrum of phytopathogenic fungi, in particular those from the classconsisting of the Ascomycetes and Basidiomycetes. Some of them have asystemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerothecafuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinulanecator in vines, Puccinia species in cereals, Rhizoctonia solani incotton, Ustilago species in cereals and sugar cane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinerea (gray mold) in strawberries and grapes,Cercospora arachidicola in groundnuts, Pseudocercosporellaherpotrichoides in wheat and barley, Pyricularia oryzae in rice,Phytophthora infestans in potatoes and tomatoes, Fusarium andVerticillium species in various plants, Plasmopara viticola in grapes,Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi. Either the fungi themselves, the soil, or theplants, seed or materials to be protected from fungus attack, aretreated with a fungicidally effective amount of the active ingredient.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins, (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as ligninsulfitewaste liquors and methylcellulose.

The fungicides generally contain from 0.1 to 95, and preferably from 0.5to 90, wt. % of active ingredient. The application rates are from 0.02to 3 kg or more of active ingredient per hectare, depending on the typeof effect desired. The novel compounds may also be used for protectingmaterials (timber),, e.g., on Paecilomyces variotii. When the activeingredients are used for treating seed, amounts of from 0.001 to 50, andpreferably from 0.01 to 10, g per kg of seed are generally required.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. A solution of 90 parts by weight of compound no. 9 and 10 parts byweight of N-methyl-α-pyrrolidone, which is suitable for application inthe form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 16, 80 parts byweight of xylene, 10 parts by weight of the adduct of 8 to 10 moles ofethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenzenesulfonic acid, and 5 partsby weight of the adduct of 40 moles of ethylene oxide and 1 mole ofcastor oil. By finely dispersing the mixture in water, an aqueousdispersion is obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 80, 40parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20parts by weight of the adduct of 40 moles of ethylene oxide and 1 moleof castor oil. By finely distributing the solution in water an aqueousdispersion is obtained.

IV. An aqueous disperson of 20 parts by weight of compound no. 225, 25parts by weight of cyclohexanol, 65 parts by weight of a mineral oilfraction having a boiling point between 210° and 280° C., and 10 partsby weight of the adduct of 40 moles of ethylene oxide and 1 mole ofcastor oil. By finely distributing the solution in water an aqueousdispersion is obtained.

V. A hammer-milled mixture of 80 parts by weight of compound no. 226, 3parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 10 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, and 7 parts by weight of powderedsilica gel. By finely dispersing the mixture in water, a spray liquor isobtained.

VI. An intimate mixture of 3 parts by weight of compound no. 246 and 97parts by weight of particulate kaolin. The dust conatins 3 wt. % of theactive ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 247, 92parts by weight of powdered silica gel and 8 parts by weight of paraffinoil sprayed onto the surface of this silica gel. This formulation of theactive ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no.251, 10 parts of the sodium salt of a phenosulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 252,2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in a greater fungicidal actionspectrum.

USE EXAMPLES

The active ingredients used for comparison purposes were1-(1,2,4-triazol-1yl)-1-phenylthio-2-methyl-2-phenylpropane (A)disclosed in EP91,219,1-(1,2,4-triazol-1-yl)-1-(4-chlorophenylthio)-2-methyl-2-phenylpropane(B) disclosed in EP 91,219 and1-methoxy-1-(1,2,4-triazol-1-yl)-2-phenylethane (C) disclosed in DE2,640,823.

USE EXAMPLE 1 Action on wheat brown rust

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dustedwith spores of brown rust (Puccinia recondita). The post were thenplaced for 24 hours at 20° to 22° C. in a high-humidity (90-95%)chamber. During this period the spores germinated and the germ tubespenetrated the leaf tissue. The infected plants were then sprayed torunoff with aqueous liquors containing (dry basis) 80% of activeingredient and 20% of emulsifier. Aftr the sprayed-on layer had dried,the plants were set up in the greenhouse at 20° to 22° C. and a relativehumidity of 65 to 70%. The extent of rust fungus spread on the leaveswas assessed after 8 days.

The results show that active ingredients 2, 80 and 247, applied as 0.025wt. % spray liquors, have a better fungicidal action (90%) than priorart comparative compounds A, B and C (40%).

USE EXAMPLE 2 Action on Botrytis cinerea

Paprika seedlings of the "Neusiedler Ideal Elite" variety were sprayed,after 4 to 5 leaves were well developed, to runoff with aqueoussuspensions containing (dry basis) 80% of active ingredient and 20% ofemulsifier. After the sprayed-on layer had dried, the plants weresprayed with a conidial suspension of the fungus Botrytis cinerea, andplaced at 22° to 24° C. in a chamber of high humidity. After 5 days, thedisease had spread to such a great extent on the untreated plants thatthe necroses covered the major portion of the leaves. Leaf attack wasassessed.

The results show that active ingredients 225 and 247, applied as 0.05wt. % spray liquors, have a better fungicidal action (85%) than priorart comparative compounds A, B and C (10%).

USE EXAMPLE 3 Action on Pyrenophora teres

Barley seedlings of the "Igri" variety were sprayed to runoff at the2-leaf stage with aqueous suspensions containing (dry basis) 80% ofactive ingredient and 20% emulsifier. After 24 hours the plants wereinoculated with a spore suspension of the fungus Pyrenophora teres andplaced for 48 hours in a high-humidity climatic cabinet kept at 18° C.The plants were then cultivated for a further 5 days in the greenhouseat 20°-22° C. and a relative humidity of 70%. The extent of fungusspread was then determined.

The results show that active ingredients 9, 16, 80, 225, 226, 246, 247,251 and 252, applied as 0.05wt. % spray liquors, have a betterfungicidal action (95%) than prior art comparative compounds A, B and C(30%).

We claim:
 1. A compound of the formula I ##STR197## where A and R¹ areidentical or different and are each C₁ -C₈ -alkyl, phenyl, biphenyl,naphthyl, benzyl, C₃ -C₆ -cycloalkyl, C₁ -C₈ -alkoxy, C₁ -C₈ -alkylthio,phenoxy, benzyloxy, phenylthio, methoxycarbonylethyl, furyl or thienyl,and these radicals may be monosubstituted to trisubstituted by halogen,nitro, phenoxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -haloalkyl,withthe proviso that at least one of the substituents A and R¹ is furyl orthienyl, each of which is unsubstituted or mono- to trisubstituted byhalogen, nitro, phenoxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄-haloalkyl, D is halogen, and X is N, or its plant-tolerated acidaddition salts or metal complex compounds.
 2. A fungicidal compositioncomprising an inert carrier and a fungicidally effective amount of anazolylethane derivative of the formula I ##STR198## where A and R¹ areidentical or different and are each C₁ -C₈ -alkyl, phenyl, biphenyl,naphthyl, benzyl, C₃ -C₆ -cycloalkyl, C₁ -C₈ -alkoxy, C₁ -C₈ -alkylthio,phenoxy, benzyloxy, phenylthio, methoxycarbonylethyl, furyl or thienyl,and these radicals may be monosubstituted to trisubstituted by halogen,nitro, phenoxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -haloalkyl,withthe proviso that at least one of the substituents A and R¹ is furyl orthienyl, each of which is unsubstituted or mono- to trisubstituted byhalogen, nitro, phenoxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄-haloalkyl, D is halogen, and X is N, or a plant-tolerated acid additionsalt or metal complex thereof.
 3. A process for combating fungi, whereina fungicidally effective amount of an azolylethane derivative of theformula I ##STR199## where A and R¹ are identical or different and areeach C₁ -C₈ -alkyl, phenyl, biphenyl, naphthyl, benzyl, C₃ -C₆-cycloalkyl, C₁ -C₈ -alkoxy, C₁ -C₈ -alkylthio, phenoxy, benzyloxy,phenylthio, methoxycarbonylethyl, furyl or thienyl, and these radicalsmay be monosubstituted to trisubstituted by halogen, nitro, phenoxy, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -haloalkyl,with the proviso that atleast one of the substituents A and R¹ is furyl or thienyl, each ofwhich is unsubstituted or mono- to trisubstituted by halogen, nitro,phenoxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -haloalkyl, D ishalogen, and X is N, or its plant-tolerated acid addition salt or metalcomplex thereof, is allowed to act on fungi, or plants, or planthabitat, plant materials, timber or seed threatened by fungus attack. 4.A compound of claim 1 wherein A is 2-thienyl, R¹ is propyl, and D ischloro.
 5. A compound according to claim 1 wherein A is 3-thienyl, R¹ isethyl, and D is chloro.
 6. A compound according to claim 1 wherein A is2-furyl, R¹ is hexyl, and D is chloro.